Dechlorination of hydrocarbons containing organic chlorine



March 23, 1954 H. J.

DECHLORINATI HEPP ON OF HYDROCARBONS CONTAINING ORGANIC CHLORINE Filed June 29. 1950 INVENTOR. H J. HEPP MM v M ATTORNEYS Patented Mar. 23, 1954 DECHLORINTION OF HYDROCARBONS CONTAINING ORGANIC CHLORINE Harold J. Hepp, Bartlesville, IOkla., assignor to Phillips Petroleum Company, a corporation of Delaware Application June 29, 1950, Serial No. 171,035

10 Claims.

This invention relates to the reduction of the organic chlorine content of hydrocarbons.

The treatment and conversion of hydrocarbons in the presence of aluminum chloride has been known and practiced for many years. Among these processes are cracking, isomerization, alkylation, lubricating oil treatment, and numerous others. These conversions yield a product containing varying small amounts of organically bound chlorine in the product; and in some in` stances, the presence of the chlorine is quite undesirable. The organic chlorine is especially undesirable in an alkylate destined for use in a spark ignition, internal combustion engine because excessive chlorine is quite detrimental to octane rating and lead response.

The organic chlorine appears to be present in paraffin alkylates as alkyl chlorides and is substantially unaffected by an ordinary caustic wash.

The reduction of chlorine content of theseI aration of the hydrocarbon and complex, and

Washing the treated hydrocarbon with water and/or an alkaline solution. The saturated hydrocarbon may be one or more present inthe feed to the process or may be one or more hydrocarbons added to the feed, e. g. an isoparafnn.

In carrying out the process, the temperature is maintained between 50 F. and 150 F., preferably between 60 F. and 130 F. The process l is carried out in liquid phase, the pressure maintained in the reaction zone being sufficiently1 high to maintain liquid phase. The reaction time is dependent on both temperature and efciency of contact of the catalyst and hydrocarbon. The reaction time is usually between 5 and 60 minutes, though under some reaction conditions, it may be outside these limits. Five to fifty volume per cent catalyst is satisfactory,

though 20 to 40 volume per cent is preferred.

The catalyst is an aluminum chloride-hydrocarbon complex having a heat of hydrolysis in the range of` 280-375 calories per gram. This type of catalyst is well known in the art as a parafn-olen alkylation catalyst.

The contact between the hydrocarbon and catalyst can be eifected in any of several ways. The contacting methods include mechanical agitation, jet agitation, circulation through tubes under turbulent iiow conditions, or other means of effectively contacting the two phases.

Following the contacting,l the two phases are preferably separated by means of gravity, though centrifuging or similar means may be employed. In gravity settling, the emulsion of catalyst and hydrocarbon is introduced into a tank wherein substantially quiescent conditions are maintained. Under these conditions, the catalyst phase settles to the bottom and is withdrawn and recycled to the reaction zone, and the hydrocarbon is removed to a caustic Washing zone. The hydrocarbon is then caustic washed to remove any dissolved catalyst or hydrogen chloride. Caustic washing is accomplished by conventional means.

The attached figure is a diagrammatic drawing of one specic embodiment of this invention wherein an alkylate produced by alkylation of isobutane with ethylene in the presence of a fluid aluminum chloride-hydrocarbon complex is treated to reduce its organic chlorine content.

Fresh isobutane is introduced through line I0, to this being added wash isobutane through line 24 and recycle butane through line I1, the combined stream then being conducted to alkylation zone I3. Also to zone I3 are added ethylene or ethylene-propylene mixtures through line Il I and aluminum chloride through line I2. This alkylation process, including reaction conditions and apparatus, is well'known to those skilled in the art and will not be described in detail here. The operations effected herein are the alkylation rei action, separation of the reactor efliuent into a hydrocarbon phase and a catalyst phase, caustic washing of the hydrocarbon phase and recycle of the requisite portion of the catalyst to the reactor. The caustic washed hydrocarbon phase is withdrawn from zone I3 through line Ill and conducted to fractionation zone I5. In this zone the hydrocarbon is fractionated to produce a propane and lighter `fraction, removed through I6 andconducted to suitable utilization not shown, an isobutane fraction which is removed through `line I'I and then recycled to the alkylation zone through line I0. The C5-I- alkylate is removed through line I8 and conducted to dechlorination contactor 20. l

The excess fluid catalyst formed in zoneMI3 is removed through line 2| and conducted to .washer 22. Here the complexiswashedfbya countercurrent stream of isobutane introduced through line 23, the isobutane stream picking up the hydrogen chloride dissolved in the complex. The Wash isobutane is removed through line 24 and conducted to line I0, then following a previously described route. The Washed complex is withdrawn through line 25 and conducted to contactor 20. In contacter 20, the fluid aluminum chloride-hydrocarbon complex is contacted with the chlorine-containing alkylate. The alkylate is comprised principally of branched-chain parains, diisopropyl being the main constituent present but there being substantial amount of isopentane andhigher-boiling branched-chain hydrocarbons. The dechlorination has been found to take place more readily in the presence of a substantial amount of isobutane or isopentane, and consequently, if isopentane is to be blended along with the dii'sopropyl to produce the nal gasoline, it isquite advantageous to add this isopentane through line i9 to contactor 22. The outside isopentane eventually to be used thus contributes a desirable effect during dechlorination as well as functioning as a blending agent when the diisopropyl is blended. The dechlorination may take place, in part, through simple alkylation of an isoparanin with the alkyl chloride yielding a higher isoparafn and hydrogen chloride. Regardless of the explanation, theadded hydrocarbon is also benecial as a diluent, thus preventing undesired molecular rearrangement or" the alkylate, especially at the higher dechlorination temperatures. Y, l y

The effluent of `contacter 20, comprising dechlorinated hydrocarbon,y catalyst and dissolved catalyst or hydrogen chloride, is `removed through line 2tV to settler 2 1. In the settler', the catalyst phase, due to its higher density, settles to the bottom andisuwithdrawn through line 28 and a major portion passed to line 25 and recycled to contacter 20. VA minor portion of the catalyst is removed through line 32 to aluminum chlorideV recovery, not shown. Only suiicient catalyst is'removed through line 32 to chloride and aluminum chloride, is removed through line 29 to caustic washing zone 3D, wherein the dissolved aluminum chloride and hydrogen chloride are removed. The washed hydrocarbon is removed from zone 30 through line 3l to suitable utilization, which may be direct blending in motor fuel, storage, or fractionation to separate the heavy allylate and subsequent blending in aviation and motor fuels and/or storage.

Example I In the runs the desired quantity of a -synthetic raw alkylate containing the proper amount of organic chlorine was prepared by mixing diisopropyl and secondary butyl chloride. This synthetic alkylate, a quantity of catalyst, and isopentane when used were introduced into a three necked 500 cc. round bottomed flask equipped with a Water cooled condenser and a mercury-seal stirrer. stirring was then begun and continued for the desired length of time. The two phases in the flask were then separated with a separatory funnel; and the hydrocarbon layer was Washed successively with distilled Water, dilute aqueous sodium hydroxide, and again with distilled Water. In the case of treatment With`zinc, the alkylate VWas refluxed while being stirred with zinc powder in the same equipment.

The chemicals used were:

(l) Diisopropyl-QQ Inol per cent minimum purity. i l (2) Isopentane-99 per cent minimum purity.` (3) A1GP-hydrocarbon complex-Contained 57 wt. per cent AlCla as determined by heat of hydrolysis. It was obtained from spent catalyst disposal of a diisop'ropyl unit.

(4) BFS-ether adduct-Used Without further purication BFsl.

(5) sulfuric acid-94.5'-95.5 727 H2804.

(6) Sed-butyl chloride-B. P. ST5-69.5 C.-'Use'd `without further purification,

(7) Zinc-CP; powdered.

45 results is attached.

DECHLORINATIN or SYNTHETIC DnsoPRoPYL ALKYLATEW WITH Alot-HYDRCCARBCN COMPLEX,

, Hzso., Bra-ETHER COMPLEX AND METALLIC ZINC C1 Con- Cl Conccs. of ccs. of Contact tent of ,gtgf Percent Tem em Run No. Catalyst Used Alkylate Composition Feed Catalyst Time` Feed, Pro-duct C1 Remil-.epa F' Used Used (Hours) wt. perwt erj moval l Concentrated H2SO4-- Pulc11 Diisopropyl-i-Sec.-Butyl 100 1.0 0.13 0.11 15 100 or e. 2.; BFa-Ether -50 DIP-i-Isopentane-l-Sec.- 100 2.0 0.112 0.106 9 80 v ButylChloride. i 3..; A1013 Sludge Pil Diisopropyl+Sec.-Butyl 1.3 0. 23 0.13 44 80 A or e. E. 4 AlCl; Sludge 50-50 DIP--Isopentane-l-Sec.- 100 1.0 0.26 0.068 74 80 Butyl Chloride. A1013 Sludge.-. .do 100 2.5 0.24 0.076 68 80 AlCh Sludge..- 100 4.5 0.22 0.070 68 80 A1013 Sludge.; 100 l. 0 0. 22 0. 045 80 8() A1013 Sludge... o 100 2.0 0.072 0.012 83 80 A1013 Sludge Diisopropyl+lsopentane but no 100 1.5 0.005 0.009 80 Sed-Butyl Chloride. 10 None Diisopropyl `50 None. 1.0 0.119 0.115 80 ll Powdered Zinc. 35 DIP-654 yDimetllylpentanes 100 l0 gms.; 1.0 0.128 0.121 9 160 +Sec.-Butyl Chloride. Y

e Passed stream of N2 through 'flash during treating period..

b A blank run to demonstrate that the AlC13-hydrocarbon complex adds no organic chlorine to the alkylatel c A blank run to demonstrate that the dilute caustic used to neutralize traces of HC1 and AlCl; does not remove organicchlorine.

maintain a constant volume of catalyst in contactor 20, for discarded alkylation catalyst continuously enters `contacter '20.

YThe hydrocarbon phase separated in settler 21, including a small ya'rno'u'nt of dS'SQlved hydrogen i It is particularly noteworthy that neither sulfuric acid nor BFs-ether "complex, runs 1 and 2, were effective to remove any real quantity of chlorine from the treated alkylate material.

s Thus, it appears to be clear that the mechanism ofthe chlorine removal reaction is not likely to be one of simple alkylation alone in View of the very well known alkylation promoting activity of the said sulfuric acid and BFs-ether complex.

The presence of HC1 during the dechlorination is apparently not harmful as shown in the following example.

Example II Disopropyl alkylate was treated with spent AlCla hydrocarbon complex in a stirred contacter for the stated length of time. At the end of this reaction period the hydrocarbon and sludge phases were separated. The hydrocarbon phase was then washed succesively with aqueous NaOH and with Water. The washed product was analyzed for chlorine.

Run A Run B 1 Temperature F. 120 80 A1013 Complex Used cc 30 60 DIP Alkylate Used. cc-. 120 200 Stix-ring Time hr.. 1.5 2.0 Chlorine in Alkylate Chargednveight percent 0. 278 0. 278 Chlorine in Treated Alkylatewcight percent 0.030 0.018 Chlorine Removal Apercent.. 89 94 l Dry HC1 was passed through the reaction zone during the course of this run.

The above data demonstrate excellent dechlorination of commercially produced alkylate in either the presence or absence of any added hydrogen chloride.

Eample II I Isobutane and ethylene, in a mol ratio of 5 to l, l were reacted by emciently contacting them with an active AlCls-hydrocarbon complex for twenty minutes at 130 F. in the presence of about '0,3 weight per cent of HC1. The resulting alkylate was washed with caustic at 130 F. and then subjected to dechlorination. 100 cc. of the caustic- Washed alkylate and 30 cc. of the AlCls-hydrocarbon complex described above were stirred together in a glass ask at 80 F. for 1.25 hours. The alkylate was recovered, washed with caustic,

and the residual chlorine Was determined. The

chlorine, it has been discovered, can be removed substantially from hydrocarbons containing them by treating said hydrocarbons with an aluminum chloride hydrocarbon complex preferably in the presence of an alkylatable hydrocarbon.

I claim:

1. In a process for the preparation of a hydrocarbon conversion product in which there is employed an aluminum chloride catalyst to effect the said conversion and in which following said conversion and after separation of the catalyst from the products of said conversion the said catalyst-free products contain residual quantities of organically-'bound chlorine, the step of contacting said catalyst-free products with an active, fluid, aluminum chloride-hydrocarbon complex catalyst, which contains free aluminum chloride, having a heat of hydrolysis in the range ci' 280-375 calories per gram to remove substantially the said residual quantities of chlorine.

2. In a process for the preparation of a hydrofil carbon conversion product in 'which there is employed an active aluminum chloride conversion catalyst to efectthe said conversion and in which` following said conversion and after separation of the catalyst from the products of said. conversion the said catalyst-free products contain small residual quantities of organically-bound chlorine, the step which comprises contacting said catalyst-free products containing said small residual quantities of organically-bound chlorine with an additional quantity of an active, fluid, aluminum chloride-hydrocarbon complex catalyst, which contains free aluminum chloride, to remove substantially the said small residual quantities of chlorine.

3. In a process for the preparation of a hydrocarbon conversion product in which there is employed an aluminum chloride catalyst to eiect the said conversion and in which following said conversion and after separation of the catalyst from the products of said conversion the said catalyst-free products contain residual quantities of organically-bound chlorine, the step of contacting said catalyst-free products with an active, iluid, aluminum chloride-hydrocarbon complex catalyst, which contains free aluminum chloride, to remove substantially the said residual quantities of chlorine.

4. A process of claim 3 in which the catalystfree products are admixed with a saturated hydrocarbon before being contacted with said aluminum chloride-hydrocarbon complex.

5. A process for the preparation of a hydiocarbon conversion product in which there is employed an aluminum chloride catalyst to eiect the said conversion and in which following the said conversion and after separation of the catalyst from the product of said conversion the said catalyst-free product contains residual quantities of organically-bound chlorine, the steps which comprise fractionating the said product into fractions each of which contains residual quantities of organically-bound chlorine and contacting one of said fractions with an active, fluid, aluminum chloride-hydrocarbon complex catalyst, which contains free aluminum chloride, to remove substantially the said residual quantity of chlorine from said fraction.

6. A process according to claim 5 wherein the said conversion product is treated with caustic to wash the same prior to the fractionation step.

'7. A process for the alkylation of an isoparafiin with an olefin in the presence of an aluminum chloride-hydrocarbon complex catalyst which comprises the steps of contacting said isoparaffin and olefin with said catalyst to prepare a hydrocarbon phase containing organicallybound chlorine, separating from said hydrocarbon phase all catalyst therein, then contacting said hydrocarbon phase containing organicallybound chlorine with an active aluminum chloride-hydrocarbon complex catalyst, which contains free aluminum chloride, to remove said residual chlorine therefrom.

8. A process according to claim '7 wherein said hydrocarbon phase is caustic washed prior to the said treatment with aluminum chloride-hydrocarbon complex.

9. A process according to claim 7 wherein an alkylate is recovered from said hydrocarbon phase, the said alkylate is caustic washed and then contacted with said aluminum chloridehydrocarbon complex.

10. The production of an alkylate product from isobutane and ethylene by contacting the 7 same in the presence of a fluid aluminum chloride-*hydrocarbon complex catalyst which comprises passing said isobutane and ethylene into contact With the said catalyst under conditions to cause alkylation of the said sobutane with the said ethylene, separating all of the said catalyst from the alkylation eluent obtained, treating said alkylation eifiuent with an alkaline washing medium, fractionating said washed alkylation efuent to obtain therefrom a fraction having a high octane value, admixing said fraction having a high octane Value with an alkylatable hydrocarbon, then contacting said fraction admixed With said alkylatable hydrocarbon with an active, fluid, aluminum chloride-hydrocarbon complex at a temperature in the range 50150 F. for 'a time in the range 5 to 60 min- References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,143,050 Berger Jan. 10, 1939 2,207,760 Russell July 16, 1940 2,288,580 Baehr June 30, 1942 2,348,701 Schmerling May 9, 1944 2,378,733 Sensel June 19, 1945 2,382,814 Proell et l. Aug. 14, 1945 2,435,621 Brooks Feb. 10, 1948 2,474,827 Condon July 5, 1949 

1. IN A PROCESS FOR THE PREPARATION OF A HYDROCARBON CONVERSION PRODUCT IN WHICH THERE IS EMPLOYED AN ALUMINUM CHLORIDE CATALYST TO EFFECT THE SAID CONVERSION AND IN WHICH FOLLOWING SAID CONVERSION AND AFTER SEPARATION OF THE CATALYST FROM THE PRODUCTS OF SAID CONVERSION THE SAID CATALYST-FREE PRODUCTS CONTAIN RESIDUAL QUANTITIES OF ORGANICALLY-BOUND CHLORINE, THE STEP OF CONTACTING SAID CATALYST-FREE PRODUCTS WITH AN ACTIVE, FLUID, ALUMINUM CHLORIDE-HYDROCARBON COMPLEX CATALYST, WHICH CONTAINS FREE ALUMINUM CHLORIDE, HAVING A HEAT OF HYDROLYSIS IN THE RANGE OF 280-375 CALORIES PER GRAM TO REMOVE SUBSTANTIALLY THE SAID RESIDUAL QUANTITIES OF CHLORINE. 